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Reaction Mechanism-I
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Chemistry : Reaction Mechanism - I ALLEN®
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REACTION MECHANISM : PART-I


 Reaction : Breaking of old bond and formation of new bond is known as chemical reaction
A B + X Y A X + B Y

Old bonds New bonds

 [A sequential account of each step, describing details of electron movement, energetics during bond cleavage
and bond formation, and the rates of transformation of reactants into products (kinetics) is referred to as
reaction mechanism. Reactants are of two types substrate and reagent.
 Substrate is that reactant which supplies carbon to the new bond and the other reactant is called reagent. If
both reactants supply carbon to the new bond then choice is arbitrary and in that case the molecule on
which attention is focused is called substrate.]
3.0 CONCEPTS TO UNDERSTAND REACTION MECHANISM :
(1) Bond cleavage (2) Attacking reagent (3) Reaction intermediate (4) Electronic effect

®
3.1 TYPE OF BOND CLEAVAGE :
(a) Heterolytical cleavage/fission : Cleavage in which unequal distribution of electrons takes place
during the bond cleavage is known as heterolytical cleavage. Due to unequal distribution of electrons,
ions are formed. That’s why it is also known as ionic cleavage or heterolytical cleavage.
(b) Homolytical cleavage/fission : Cleavage in which equal distribution of e–s takes place during the
chemical reaction is known as homolytical cleavage.
Due to equal distribution of electrons, without charge unpaired electrons species is formed, which is
known as free radical and cleavage is known as unionic cleavage/homolytical fission.

C + ×. Z
Ionic cleavage
or

C .× Z C .× + Z Heterolytic fission

Un ionic cleavage
C . + × Z or
Homolytic fission
Reaction
intermediate

3.2 TYPES OF ATTACKING REAGENTS

These are of two types :
(a) Electrophilic reagent or electrophiles:
Electrophilic (electro + philic)
(electron + loving)
The reagent which attacks on the negative part of the molecule or loves electrons are called electrophiles.
Electrophiles may be positively charged or neutral.
(i) Positively charged electrophiles :
       
H , SO3 H , NO , NO2 , X , R , R C , C6 H5 — N2
O
(ii) Neutral electrophiles :- central atom e– deficient
(a) All Lewis acids as :
BF3, AlCl3, SO3, ZnCl2, BeCl2, FeCl3, SnCl2, CO2, SnCl4.
(b) Free radicals, carbenes and nitrenes act as electrophiles.
51
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(b) Nucleophilic reagent or nucleophiles
Which attacks on the positive site of the substrate or loves nucleus.
Nucleophilic (Nucleo + philes)
        
(Nucleus + loving)
Nucleophiles may be negatively charged ions or posses a lone pair of electron or e–.
(i) Negatively charged nucleophiles.
s s s s s s s s s
H, O H, O R, C N, X, R, R-CO O, N H2 , S H
(ii) All Lewis base which contains lone pairs or e–
     
H2 O

, RO

H, RO

 R , N H3 , R  N H2 , R 3 N , CH2=CH2, CHCH.

(iii) R – Mg – X, LiAlH*4 ,NaBH*4

®
The star (*) indicates the atom which donates electrons to the substrate.
Ambident nucleophile :- Nucleophiles which have two sites of electron rich centre or in which two or
more atoms bear a lone pair of electrons.

Examples :- K O–N=O, NH2–OH, NaCN
  



3.3 REACTION INTERMEDIATE

 Carbocation :
Cation in which positive charge is present on carbon atom is called carbocation.
  Due to electron deficiency it acts as an electrophile and always attack on electron richer site.
  It is incomplete octet species because it has six electron in outer most shell.
  All electrons are paired.
 Carbanions : Anion in which negative charge is present on carbon atom is called carbanion.
  It has eight electron in outermost shell so it is complete octet species.
  It is an electron richer species because it has extra electron.
  Due to presence of non bonding electrons it acts as a nucleophile.
 Free Radical :
  Electrically neutral species in which unpaired electron is present on carbon atom is known as carbon
free radical.
  It has seven electron or odd electron in outermost shell.
  It is incomplete octet species so it is also electron deficient species.
 Carbenes (CH2:) :
Carbenes are neutral carbon species in which the carbon atom is bonded to two monovalent atoms or
groups and carries two nonbonded electrons.
 It behaves as an electrophile.  6 e– in outermost shell.
 It is neutral.   4 e– are bonded and two are nonbonded e–.

 Nitrenes (– N :)
Nitrenes are neutral nitrogen species in which the nitrogen is bonded to one monovalent atom or group and
carries four non-bonded electrons.
 It is monovalent radical.  6 e– in outermost shell.
 It is neutral.  Two are bonded and four are nonbonded electrons.
52
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BEGINNER'S BOX-1
1. Which of the following species is not electrophilic in nature :-

 
(1) BH3 (2) H3 O (3) NO2 (4) Cl

2. CH3CH2–Cl undergoes homolytic fission to produce :-

  
(1) CH3 C H2 and C l (2) CH3 C H2 and Cl Θ

 Θ
(3) CH3 C H2 and Cl Θ (4) CH3 C H2 and Cl 

3. Which of the following intermediate has complete octet :-

®
(1) Carbocation (2) Carbanion (3) Free radical (4) Carbene

3.4 ELECTRONIC EFFECTS :

There are four effects which affect the chemical reaction due to transfer of electron

(1) Inductive effect (2) Mesomeric effect

(3) Hyperconjugation (4) Electromeric effect

3.4.1 INDUCTIVE EFFECT (I-EFFECT) :

 Polarity induced in non polar  bond due presence of adjacent polar bond is known as inductive effect.

GOLDEN KEY POINTS

 In I-effect there is partial displacement of e1.
 After 3 or 4 C-atom I-effect is considered to be zero.
 Inductive effect decreases on increasing distance.
∝

1
So Magnitude of I effect
distance

 I-effect of hydrogen is considered as zero.

–I groups :
2
   O sp
sp
— OR 2 > — NR 3 > — N H3 > –N > C  N > C OH
O
O

—X > –OR > –OH > –CCH > —NH2 > C6H5 > – CH = CH2

+I groups :

CH3
Θ Θ Θ
 N H >  O >  COO > –C–CH3 > –CH–CH3 > —CH2–CH3 > —CD3 > —CH3
CH3 CH 3

53
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APPLICATION OF I-EFFECT
(1) Stability of carbocation :

1
Energy  charge 
stability

 I effect
Stability of carbocation 
 I effect

CH3
   
Example : Stability order : : (1) CH3 C > (2) CH3 CH > (3) CH3 CH2 > (4) CH3
CH3 CH3
3° 2° 1°

®
Reason : More no. of +I group.
more stable carbocation.
so stability order 1 > 2 > 3 > 4.
(2) Stability of carbanion :

 I effect
Stability of Carbanion 
 I effect

CH3
1 1 Θ
Example: : (1) CH3 1 (2) CH (3) CH3 CH2 (4) CH3
C CH3
CH3 CH3
3° 2° 1°

  More No. of +I group.

   Less stable carbanion.
So stability order 4>3>2>1
1 1 1
Example : (1) CH2 CH CH2 CH3 (2) CH2 CH2 CH CH3 (3) CH2 CH2 CH2 CH2 F
F F

 Minimum distance of –F.

  Maximum –I of –F.
Minimum negative charge.
 Maximum stable.
So stability order 1 > 2 > 3
Θ Θ Θ
Example (1) CH2  CH2 F (2) CH2  CH2 OH (3) CH2  CH2 NH2

 Maximum –I of F.
 Negative charge will be minimum.
 Maximum stable.
So stability order 1 > 2 > 3
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BEGINNER'S BOX-2
1. Most stable carbocation is :

   
(1) CH3  CH2 (2) Br  CH2  CH2 (3) Cl  CH2  CH2 (4) F  CH2  CH2

2. Most stable carbanion is :

Θ Θ
(1) CH2  CH2  NO2 (2) CH2  CH2  CN

Θ Θ
(3) CH2  CH2  COOH (4) CH2  CH2  CH2  CH2  F

(3) Acidic and basic strength :

®
 Acidic strength :

+
H donor
Acid
–
e acceptor

– I effect
Acidic strength  Stability of conjugate base (anion) 
 I effect

Example :

(i) CH3–CH2–COOH < Cl–CH2–COOH < F–CH2–COOH

 
–H –H –H

CH3–CH2–COO Cl–CH2–COO F–CH2–COO

+I of –CH3 Maximum –I of –F

anion is less stable Maximum stable anion

Corresponding acid is maximum acidic.

(ii) CCl3—COOH > CBr3—COOH > CI3—COOH

maximum –I of Cl

so maximum acidic.

(iii) CH3–CH2–CH–COOH > CH3– CH–CH2–COOH > CH2– CH2–CH2–COOH

F F F

minimum distance of F from –COOH

maximum –I of F.

So maximum acidic.
55
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(iv) CH2–COOH > CH2–COOH > CH2–COOH
NO2 H CH3
–I of NO2 +I of –CH3
maximum acidic
(v) HCOOH > CH3—COOH > CH3—CH2—COOH
maximum +I
minimum acidic
COOH CH2–COOH
(vi)   COOH  
CH2
COOH COOH CH2–COOH
minimum distance of –COOH from other
maximum –I of –COOH on other
maximum acidic
CH4 NH3 H2O HF

®
  
(vii) –H < –H < –H < –H

CH3 NH2 OH F
Negative charge on maximum E.N.
Maximum stable anion
So corresponding acid is most acidic
CHCH CH3–CCH NH3 CH3–NH2
(viii) 
–H > –H > 
–H > –H

CHC CH3–CC NH2 CH3–NH

negative charge on more EN +I of –CH3 +I of –CH3

atom and no +I
anion is maximum stable
so corresponding acid is most acidic
CH3SH CH3–OH
(ix) –H > –H

CH3S CH3–O
negative charge on big size atom
more stable anion
so corresponding acid is more acidic
 Basic strength :
–
OH donor
Base –
e donor
+
H acceptor

+ I effect
Basic strength 
–I effect

Ex.: (1) CH3NH2 (2) C2H5NH2 (3) C3H7NH2 (4) C4H9NH2

Ans. 4 > 3 > 2 > 1 Maximum +I
so maximum basic
56
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BEGINNER'S BOX-3
1. Which of the following is most acidic :

(1) Cl3C—COOH (2) Cl2CH—COOH (3) ClCH2—COOH (4) CH3COOH

2. Which of the following is most acidic :

(1) CH2—COOH (2) CH2—COOH (3) CH2—COOH (4) CH2—COOH

F Cl Br I
3. Which is most basic among the following :

(1) CH3CH2–NH2 (2) Cl–CH2CH2NH2

(3) O2N–CH2CH2–NH2 (4) CH3–CH2CH2–NH2

3.4.2 RESONANCE OR MESOMERIC EFFECT

®
Delocalization of  e– is called as resonance or complete transfer of e– from one shell to another shell is
called as Resonance.

Conditions For Resonance

(1) If there are two bonds in conjugation then e– of one bond are transferred towards another bond.

(a)
 Θ Θ 
Ex. (i) CH2=CH–CH=CH2    CH2  CH  CH  CH2    CH2  CH  CH  CH2
(b) (a) (b)


(ii) CH2=CH–C–H CH2–CH=C–H
O O
(2) If there is lone pair or a negative charge and  bond are in conjugation then e– of lone pair or negative

charge are transferred towards  bond.


Ex. (i) CH2=CH–OH CH2–CH=OH

(ii) CH2=CH–CH2 CH2–CH=CH2

(3) If there is positive charge (vacant orbital) and  bond are in conjugation then e– of  bond are

transferred towards positive charge.

 
Ex. CH2=CH–CH2 CH2–CH=CH2

(4) If there is free e– and  bond are in conjugation.

Ex. CH2=CH–CH2 CH2–CH=CH2

(5) If there is lone pair or negative charge and positive charge (vacant orbital) are in conjugation then e– of

lone pair or negative charge are transferred towards positive charge.

  
Ex. (i) CH2–OH CH2=OH (ii) CH2—CH2 CH2=CH2

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GOLDEN KEY POINTS

 –
In resonance only e are transferred not atoms.

 The number of e– or number of unpaired or paired e– in all resonating structures should be same.

 It is permanent effect.

 All the resonating or canonical structures must follow the Lewis structures.

Draw resonating structures :

  
1. OH OH OH OH OH

5-Resonating structures

®
CH2 CH2 CH CH2 CH2
2.

5-Resonating structures
  
CH2 CH2 CH2 CH2 CH2
3.  

5-Resonating structures

C–H C–H C–H C–H C–H
4.  
O O O O O

5-Resonating structures
M-effect of two types :

(1) + M-effect :- To donate electrons in resonance.

+M group : Lone pair containing group like

 NHCOCH ,OCOCH
        
 NH2 ,  OH,  OR,  NR 2 ,  SH,  NHR, X , 3  3


eg. OH OH

–OH group lone pair donor

So + M of –OH group

(2) – M-effect :- To withdraw electrons in resonance.

–M group : —CHO, —COOH, —COOR, —COR, —NO2, —CN, —COX, —CONH2, —SO3H

eg. C–H C–H


O O

–CHO group withdrawing e–.

So –CHO is –M group

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BEGINNER'S BOX-4
1. Which of the following compound show resonance :-
   O 
(1) CH2  C  N (2) CH2  CH  O (3) CH2–N (4) CH2  CH  NH3
O

2. Which of the following compound show +M effect ?

O 
(1) –N (2) —CN (3) —CH=O (4) —NH2
O

APPLICATIONS OF RESONANCE EFFECT :

(1) Stability of carbocation.

Ex. Give stability order for :-

®
  
(i) CH2  CH  CH2 > CH3 CH2–CH2 > CH2=CH CH–CH2

stable by +I of Alkyl group –I of Alkenyl group

resonance (SBR)
  
(ii) CH3–C–CH=CH2 > CH3  CH  CH  CH2 > CH2  CH  CH2

CH3

SBR and +I of two –CH3 SBR and +I of one –CH3 SBR only
     
(iii) (C6H5)3 C > (C6H5)2 C H > C6H5 C H2 > CH2=CH— C H2 > (CH3)3 C > (CH3)2 C H >

   
CH3— C H2 > C H3 > CH2= C H > CH  C

  
(iv) CH2 < CH2 < CH2

maximum resonance
  
CH2 CH2 CH2
(v) > >

SBR SBR No. reso.

and + I and – I
  
(vi) > >

more resonance less resonance localized charge

 
(vii) CH2–C–H < CH2–CH2–C–H

O O

No reso. No reso.
more –I of —CHO less –I of —CHO
so less stable
59
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(2) Stability of carbanion :

Ex. Give stability order of :

Θ Θ Θ
(i) I. CH2  CH  CH2 II. CH2  CH III. CH3  CH2

SBR negative on more EN

stability order I > II > III
Θ Θ Θ Θ Θ Θ Θ Θ
(ii) (C6H5)3 C > (C6H5)2 CH > C6H5 CH2 > CH2=CH– CH2 > CH3 > CH3– CH2 > (CH3)2 CH > (CH3)3 C

(iii) I. II. III.

resonance stable more resonance stable localized 1 charge

®
stability order II > I > III
Θ Θ Θ
(iv) I. CH2 —NO2 II. CH2 —CH2—NO2 III. CH3— CH —NO2

SBR no. reso SBR but +I of CH3

stability order I > III > II

(v) I. II. CH2 III. CH3

SBR and +I SBR SBR and more +I

stability order II > I > III

(3) Stability of free radicals.

Ex. Give stability order for :

  
(i) I. CH2  CH  CH2 II. CH3 – CH2 III. CH2  CH  CH CH  CH2

less resonance no resonance more resonance

stability order III > I > II
     
(ii) (C6H5)3 C > (C6H5)2 CH > (C6H5) CH 2 > CH2=CH— CH 2 > (CH3)3 C > (CH3)2 CH >
 
CH3 CH 2 > CH 3

(4) Stability of resonating structures (R.S) Rules :

(i) Complete octet R.S. is more stable than incomplete octet.

(ii) Nonpolar R.S. is more stable than polar resonating structures.
(iii) For charged R.S. negative charge on more EN and positive charge on less EN is more stable.

Ex. Arrange the following for stability order.

 
(i) R–C–OH     R–C=O–H     R–C–OH  
O O O

complete octet, nonpolar complete octet, polar incomplete octet

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
 (ii) R–C–OH    R–C–OH

O O
less EN atom more EN atom with
with incomplete octet incomplete octet

 
(iii) R–C=O < R–CO
incomplete octet complete octet
Θ Θ
(iv) CH2  CH  O > CH2 – CH  O
(negative charge on (negative charge on
more EN) less EN)

BEGINNER'S BOX-5

®
1. Arrange the following intermediate in their stability order ?

  +
(A) CH2  CH — CH2 (B) CH2  CH — CH — CH  CH2 (C) CH2=CH—C—CH=CH2
CH
CH2

(1) A > B > C (2) C > B > A (3) B > C > A (4) A > C > B

2. Arrange the following resonating structure in their stability order :-

+ + +
(A) CH2=CH–CH=O (B) CH2–CH–CH=O (C) CH2–CH–CH–O (D) CH2–CH=CH–O

(1) A > B > C > D (2) D > C > B > A (3) A > C > D > B (4) D > C > A > B

(5) Aromaticity : Conditions for a compound to be aromatic

(a) Compound should have cyclic resonance.

(b) It should follow Huckel's Rule :- [4n + 2] electrons. (Odd number of electron pairs)

n=0 2 electrons or 1 pair

n=1 6 electrons or 3 pairs

n=2 10 electrons or 5 pairs

n=3 14 electrons or 7 pairs

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S.No Compound Cyclic Plannar Cyclic Huckel Aromatic

Resonance Rule Yes/No
(4n+2) e –


1.    2e– Yes

1
2.    4e– No

3.    4e– No

4.    6e– Yes

®
5.    6e– Yes

6.    4e– No


7.    6e– Yes

8. ..    6e– Yes
O
..

9.
..
   6e– Yes
S
..

10. ..
N
   6e– Yes

11.    6e– Yes

..
N

12.    10e– Yes

13.    14e– Yes


N
14.    6e– Yes
N


15.    6e– No

16.    6e– + 6e– Yes

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BEGINNER'S BOX-6

1. Which of the following is nonaromatic

(1) (2) (3) (4)

2. Which of the following compounds are aromatic in nature

NH2

(a) (b) (c) (d)

O
N

(1) Only a (2) a and b (3) a,b,d (4) all of these

3. Which of the following is not aromatic compound

®
O
C
(1) N (2) (3) O (4) All of these
N C
H
O

(6) Acidic and Basic strength :

 M,  I 
(a) Acidic strength :  Acidic strength  stability of conjugate base (anion)  
 M  I 

Illustrations
Illustration 1. Carboxylic acids are more acidic than phenols, why ?
Solution.
R–C–OH OH
O
–H –H

R–C–O R–C=O O O
O O

2, equal R.S. more stable anion 5, unequal R.S. less stable anion
so corresponding acid is more acidic.
Here, carboxylate ion is more stable than phenoxide ion.
Note : The molecule having equivalent R.S. has more stability than the molecule having non equivalent R.S.

Illustration 2. Phenol is more acidic than alcohols why ?

Solution. Ph–OH R–OH

–H –H

Ph–O (Phenoxide ion) R–O (Alkoxide ion)

anion stable by resonance no resonance.

So, corresponding acid is more acidic. less stable anion
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(b) Basic strength order :- If there is more resonance of lone pair or negative charge then it will be more
stable, means less basic.
  M,  I 
 Basic strength  H accepting tendency  l.p.donating tendency  M  I 
 
Ex. Give basic strength order :

(i) NH2 CH2–NH2 NH–CH3

I II III
l.P. is stabilized by no reso. of l.p. l.p. is stabilized by resonance
resonance so maximum basic and +I of CH3
basic order — II > III > I

(ii) NH2
N N

®
H
I II III
localized l.p. localized l.p.
SBR on more EN on less EN
basic order — III > II > I

(iii) < NH2

N
H
more resonance of l.p. less resonance of l.p.
so less basic so more basic
H

N
O
(iv) N N
N N
H H
I II III IV
l.p. on more –I +I less – I of
more EN of oxygen nitrogen
so minimum basic
So, basic order III > IV > II > I

Illustrations
Illustration 3. Give stability order of :
  

CH2 CH2 CH2 CH2

(i)

(–M) NO2 (–I) Cl (+I) CH3 (+M) OCH3

I II III IV
charge  charge  charge  charge 
So stability order IV > III > II > I

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  
 CH2 CH2 CH2
CH2

NO2
(ii)
NO2
NO2
I II III IV
–MO = –MP and –Mm = 0
but –IO > –Im > – IP , –M and –I increases positive charge.
stability order is IV > II > III > I
 
 CH2 CH2 
CH2 CH2
OH
(iii)
OH
OH

®
I II III IV
–OH group shows +M effect
+ MO = + MP and + Mm=0 but –IO > –Im > –IP and + M >> – I
So +M stabilize the carbocation by decreasing positive charge
Stability order III > I > IV > II

CH2 CH2 CH2 CH2

(iv)

(–M) NO2 (–I) Cl (+I) CH3 (+M) OCH3

I II III IV
charge  charge  charge  charge 
stability order I > II > III > IV

CH2 CH2 CH2 CH2

NO2
(v)
NO2
NO2
I II III IV
–M and M=0 –M and
more –I only –I less –I
charge is minimum
So stability order I > III > II > IV
Illustration 4. Give acidic strength order for :
OH OH OH OH

(i)

NO2 Cl CH3 OCH3

I II III IV
–M –I +I +M
So acidic order is I > II > III > IV
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OH OH OH OH

NO2
(ii)
NO2
NO2
I II III IV
–M and M=0 –M and
more –I only –I less –I
Acidic order should be I > III > II > IV but correct order is III > I > II > IV
Reason : Due to intramolecular H-bonding in ortho nitrophenol, it is less acidic than para
nitrophenol.
OH O=N O
OH
O

®
N
O
O N=O H=O
 intramolecular H-bonding intermolecular H-bonding
less association more association
 less B.P. more B.P.
more volatile less volatile
less acidic more acidic
 less soluble in water. more soluble in water.

OH OH OH OH
NO2 NO2
(iii) NO2 NO2

NO2 NO2
I II III IV
maximum –M and
maximum –I effect
so maximum acidic
Acidic order I > II > III > IV
COOH COOH COOH COOH COOH

(iv)

NO2 Cl CH3 OH
I II III IV V
–M –I +I +M
acidic order is I > II > III > IV > V
(v) H—COOH CH3COOH C6H5—COOH
I II III
Acidic order is I > III > II
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COOH COOH COOH
COOH
NO2
(vi)
NO2
NO2

ortho effect only –I –I and –M

Acidic order is  o > p > m > benzoic acid

COOH COOH COOH COOH

CH3
(vii)
CH3
CH3

®
ortho effect only +I +I and +H

Acidic order is  o > benzoic acid > m > p

Illustration 5. Give basic strength order for :

NH2 NH2 NH2 NH2

(i)

NO2 Cl CH3 OCH3

I II III IV

–M –I +I +M

Basic strength order IV > III > II > I

NH2 NH2 NH2

NH2
CH3
(ii)
CH3
CH3

SIP only +I +H and +I

Basic strength order is  p > m > aniline > o

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BEGINNER'S BOX-7
1. Most acidic among the following is :

(1) OH (2) CCH (3) OH (4) OH

2. Which nitrogen is maximum basic :-

3
C–NH2
1
H–N O
NH
2

(1) 1 (2) 2 (3) 3 (4) All are equally basic

®
3. Which is strongest base ?

(1) pyrole (2) Aniline (3) Pyridine (4) N

H

4. Which is weakest base :

(1) C6H5—CH2—NH2 (2) C6H5—CH2—NH—CH3
(3) O2N—CH2—NH2 (4) CH3—NH—CHO

3.4.3 HYPERCONJUGATION EFFECT (H-EFFECT)

Complete transfer of e– of C–H bond towards bond or positive charge or free electron is called as
H-effect (permanent effect). It is also called as No bond resonance and given by Nathen and Baker.
 CONDITIONS OF H-EFFECT :
1. If there is C–H bond and positive charge are in conjugation
 Carbon which is attached to positively charged carbon is called as  –C and H which is attached to 
–C is called as – H. So if number of – H is more than there will be more number of hyperconjugating
structures, so more stable carbocation.

H H H H
 
H C CH2  H C CH2  H C CH2  H 
C CH2

H H H H

all are called as hyperconjugating structures or canonical structures.

2. If there is C–H bond and free e– are in conjugation then there will be H-effect.

Carbon, which is attached to C having unpaired e–, is called as –C and H which are attached to -C are

called as -H.

H H H H

H C CH2  H C CH2  H C CH2  H C CH2
H H H H
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3. If there is C–H  bond and  bond are in conjugation then there will be H-effect.

Carbon which is attached to double bonded C is called as –C and H attached to –C is called as –H.


H H H H
 1 1  1
H C CH CH2  H C CH CH2  H C CH CH2  H C CH CH2
H H  H
H

Note : If there is C—H  bond and negative charge in conjugation then there will be no H-effect.

H
1
H C CH2 (No H - effect)
H

®
no shifting of C—H  bond, because anion is having complete octet. (8e–)

 APPLICATION OF H-EFFECT

 Stability of carbocation / Free Radical /Alkene

 Stability  No. of canonical structures  No. of  H.

Example : Give stability order for :-

CH3
 
(i) CH3 C* > CH3 *
CH > CH3  CH2 > CH3 (* = +/)
CH3 CH3

9 -H 6 -H 3 -H Zero -H

Maximum stable
*
(* = +/)
* CH3 * CH
(ii) > > 2

7 -H 4 -H 1 -H

Maximum stable

(iii) CH3—CH=CH2 > CH2=CH2

3 -H Zero -H

more stable

(iv) Stability order of alkenes will be

CH3 CH3 CH3 CH3 CH3 H CH3 H

C C C C C C C C
CH3 CH3 CH3 H CH3 H H CH3

CH3 CH3 CH3 H H H

C C C C C C
H H H H H H

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

GOLDEN KEY POINTS

 Heat of hydrogenation :

R—CH=CH2 + H2 R—CH2—CH3 + H (Heat of hydrogenation)

Heat evolved when any unsaturated hydrocarbon is hydrogenated is called heat of hydrogenation (H)

 If alkene is more reactive towards hydrogen then it will evolve more H.

1 1
So, Heat of hydrogenation  
stability of alkene number of  H

BEGINNER'S BOX-8
1. Which of the following alkene is maximum stable (R=CH3)

®
(1) R2C=CR2 (2) R—CH=CR2 (3) R—CH=CH—R (4) R—CH=CH2

2. Which of the following has minimum heat of hydrogenation.

(1) ethene (2) Propene (3) cis-2-butene (4) trans-2-butene

3. What is the order of acidic strangth of given molecules

OH OH OH OH
CH3
(I) (II) (III) (IV)
CH3
CH

(1) I > II > III > IV (2) IV > III > II > I (3) IV > II > III > I (4) I > II > IV > III

3.4.4 ELECTROMERIC EFFECT : (E Effect)

Complete transfer of a shared pair of -electrons to one of the atoms on the demand of an attacking reagent

is called as E-effect

(i) Positive Eelctromeric Effect (+ E effect) : In this effect the -electrons of the multiple bond are
transferred to that atom to which the reagent gets attached. For example :


C=C + H+ C–C
(attacking H
reagent)

(ii) Negative Electromeric Effect (-E effect) : In this effect the - electrons of the multiple bond are
transferred to that atom to which the attacking reagent does not get attached. For example.

C=O + CN C–O
(attacking
reagent)
CN

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Shifting of  electrons :


reagent
(i) CH2=CH2  CH2=CH2


reagent
(ii) CH3–CH=CH2   CH3–CH–CH2
+I

(a)
 
reagent
(iii) CH3–CC–CH3   CH3–C=C–CH3 or CH3–C=C–CH3
(a) (b)
(b)


reagent
(iv) CCl3–CH=CH2   CCl3–CH–CH2
–I

3.5 TAUTOMERISM OR DESMOTROPISM

 Tautomers have same molecular formula but different structural formula due to migration of active hydrogen

®
between two atoms of a molecule.

 Desmotropism means bond turning. [Desmos = Bond ; Tropos = Turn]

CH2–C–H
–H of carbonyl compound is active H
H O
–Hydorgen or active H

H H
Ex. H–C–C–H H–C=C–H
H O O–H

Ex. CH3–C–CH2 CH3–C=CH2

OH O–H
keto ene + ol = enol

Note : (1) Tautomers are also F. I. and exist in dynamic equilibrium.

(2) By shifting of H–atom, bond also changes its position.

(I) Condition for Tautomerism :

(a) For carbonyl compounds :- Carbonyl compounds having at least one active-H(–H) show tautomerism

(i) CH3–C–H 3 H, shows tautomerism.

O

 (ii) CH3–C–CH3 6 H, shows tautomerism

O

(iii) CH3–CH–C–H 1 H, shows tautomerism

CH3 O

(iv) H–C–H No H, No tautomerism

O
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O
C–H
(v) No H, No Tautomerism

O
(vi) C–CH3 (Acetophenone) 3 H, shows tautomerism (Acetophenone)

(vii) Ph–C–Ph (Benzophenone) No H, No tautomerism (Benzophenone)

O

®
(viii) Ph–C–CH2–C–Ph 2 H, shows tautomerism
O O

O
H H
(ix) 4 H, shows tautomerism
H H

O
H H
(x)  H, attached sp2 carbon does not initiate in tautomerism
H H
O

(b) For nitro compounds : Nitro compounds having at least one active-H (– H) show tautomerism

O O
CH2–N CH2=N
O OH
H
Nitro form Acinitro form
(acidic form so soluble in base)

(c) H–CN and H–N C are tautomers [also Functional isomers] while R–CN and R–N C are only

Functional isomers.

H–CN 

 C N–H

Active H

O
(d) H–N and H—O—N=O are tautomers.
O

Note : Nitro compounds with at least one –H are soluble in NaOH.
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BEGINNER'S BOX-9
1. Which of the following does not show keto enol tautomerism.

O O
H
(1) (2) H
O
O

O
CH=CH–OH
(3) (4)

2. Which of the following is not soluble in NaOH.

®
(1) CH3CH2—NO2 (2) (CH3)2CH—NO2

(3) (CH3)3C—NO2 (4) Ph—CH2—NO2

(II) Enol Content :

1. CH2–C–H 
 CH2=C–H
H O OH

"keto" (99%) "enol" (1%)

O OH
H 2
 sp
2. 

"keto" (1%) "enol" (stable by resonance and aromatic nature) (99%)

GOLDEN KEY POINTS

 More active the H, more will be its participation in tautomerism.

 Stability of enol form depends on (i) Resonance and (ii) H – Bond (iii) Aromaticity.

BEGINNER'S BOX-10
1. Which has maximum enol content :

(1) CH3–C–H
O

(2) CH3–C–CH3
O

(3) CH3–C–CH2–C–OC2H5
O O

(4) CH3–C–CH2–C–CH3
O O
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2. Which has maximum stable enol form
O OH O OH
H H
(1) 

 (2) 


H

O OH OH
O
(3) 

 (4) 


O OH

BEGINNER'S BOX-1
Que.
Ans.
1
2
ANSWER KEY
2
1
3
2
®
Que. 1 2
BEGINNER'S BOX-2
Ans. 1 1

Que. 1 2 3
BEGINNER'S BOX-3
Ans. 1 1 4

Que. 1 2
BEGINNER'S BOX-4
Ans. 3 4

Que. 1 2
BEGINNER'S BOX-5
Ans. 2 3

Que. 1 2 3
BEGINNER'S BOX-6
Ans. 4 4 3

Que. 1 2 3 4
BEGINNER'S BOX-7
Ans. 3 2 4 4

Que. 1 2 3
BEGINNER'S BOX-8
Ans. 1 4 3

Que. 1 2
BEGINNER'S BOX-9
Ans. 3 3

Que. 1 2
BEGINNER'S BOX-10
Ans. 4 4
74